CN1410466A - Organic ester hardening alkaline phenolic resin and its preparation method - Google Patents
Organic ester hardening alkaline phenolic resin and its preparation method Download PDFInfo
- Publication number
- CN1410466A CN1410466A CN 01127451 CN01127451A CN1410466A CN 1410466 A CN1410466 A CN 1410466A CN 01127451 CN01127451 CN 01127451 CN 01127451 A CN01127451 A CN 01127451A CN 1410466 A CN1410466 A CN 1410466A
- Authority
- CN
- China
- Prior art keywords
- organic ester
- phenolic resin
- resin
- ester hardening
- alkaline phenolic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
An organic ester hardened alkaline phenolic resin as the organic adhesive for casting is disclosed. Its primary component is methyl phenolic resin prepared by polycondensation between monophenol, biphenol and aldehyde compound (fatty aldehyde). Its advantages are low viscosity, low free formaldehyde (lower than 0.1%), low free phenol (lower than 0.2%), and low poison.
Description
The present invention relates to a kind of preparation method and application of self-hardening property mold adhesive composition, has proposed a kind of synthetic method of alkalescent phenol resin of novelty especially.
This resin is applicable to so-called self-hardening property organic ester cold-box, and the mixture after fire-resistant sand grains, alkalescent phenol resin and organic ester hardening agent are mixed charges into sclerosis shaping in the cast pattern.The stiffening agent that this alkalescent phenol resin is suitable for is an organic ester, comprises monoacetin, glyceryl diacetate, triacetin etc.
Organic ester hardening alkaline phenolic resin sand (Alpha-set) is a kind of new resin self-setting sand technology that the eighties is risen.This technology has overcome organic cold-hardening resin sand (No-bake) and cold box resin sand technologies such as (Cold-box) at the scene after the problem of aspect such as operating mode and environmental pollution, this technology has obtained bigger breakthrough, and compare with other self-hardening sands, ester sclerosis alkalescent phenol resin sand is not owing to contain elements such as N, S, P, thereby eliminated some casting flaws that caused by these elements.In addition, this technology is produced special steel casting owing to can be applicable to the higher alkaline sand of consumption acid number, has the secondary hardening phenomenon is applied to alloy components with have advantage such as good collapsibility in the time of 500 ℃ production, has further enlarged its application and promotional value.
Obtain the product of existing application and in recent years patent and document analysis from market, this resinoid exists the viscosity height both at home and abroad at present, and greater than 150mpa.s/25 ℃, smell is bigger, and curing speed is slow, the low product defects that waits of specific tenacity.
The objective of the invention is to solve the defective of above existence, a kind of alkalescent phenol resin of self-hardening property organic ester hardening is provided.
The objective of the invention is to be realized by following technical scheme: the alkalescent phenol resin main body is a resole, has materials such as alkali (KOH or NaOH), water, a spot of phenol, aldehyde in this system.Because the existence of alkali makes that the resole in the system mostly exists with phenol negative oxygen ion form, the Sn2 nucleophilic reaction easily takes place under the effect of organic ester, at first generate unsettled intermediate, then change multidirectional crosslinked build superpolymer into.In reaction process, organic ester is a stiffening agent, is again catalyzer, and it participates in entire reaction, and finally is contained in the high polymer system.In the speed of reaction of resin solidification and the stiffening agent in the content of ester and the binding agent concentration of phenol negative oxygen ion relevant, ester content is high more, phenol negative oxygen ion concentration is big more, reacts fast more.
We use infrared spectra and verify for this hardening mechanism, the results are shown in Figure 1 (uncured resin spectrogram) and Fig. 2 (resin molding spectrogram behind the resin solidification).The variation of the functional group before and after we solidify as can be seen from Fig. 1 and Fig. 2, and then can infer and resin in solidification process, formed the molecular chain of the unsettled three dimensional structure that contains a large amount of ehter bonds, the further polymerization when being heated of the molecular chain of these unsettled three dimensional structures forms the molecular chain of stable three dimensional structure.
We adopt following scheme to realize the present invention by mechanism:
(1) the interior fluctuation that is distributed in of molecular weight helps the sclerosis of binding agent, the reduction and the storage of viscosity;
(2) impel the phenolic hydroxyl group in the molecular chain how to exist, help keeping the resin activity with the negative oxygen ion attitude;
(3) exist in the maintenance system under the condition of certain phenolic hydroxyl group, the methylene ether link in the resin is increased, the viscosity that helps binder system is improved, and is beneficial to the control of free phenol, free aldehyde;
(4) adopt the ketone properties-correcting agent participation system reaction that is fit to, improve speed of reaction.
The method of the synthetic alkalescent phenol resin of the present invention can be effectively be reduced to the viscosity of this resinoid below 90 centipoises/25 ℃, has obviously improved the sand grains mixture homogeneity; And the free formaldehyde that can control this adhesive composition is less than 0.1%, and free phenol has effectively reduced the toxicity of such binding agent less than 0.2%.
Fig. 1 is uncured alkalescent phenol resin infrared spectrogram in the accompanying drawing; Fig. 2 is a resin molding infrared spectrogram behind alkalescent phenol resin and the organic ester mixed hardening.
This organic ester hardening alkaline phenolic resin synthetic proportioning and synthetic method are as described below:
(1) proportioning (weight ratio): aldehydes (37.0%): 800～900 parts of phenols (99.0%): 450～550 parts of properties-correcting agent (98.0%): 20～40 parts of liquid caustic soda (50%): 550～650 parts
(2) synthetic method:
Drop into aldehydes, phenols, properties-correcting agent, start and stir, add a step liquid caustic soda, be warming up to 60 ℃, pick up counting, and drip two step liquid caustic soda, dropwise in 30 minutes, be warming up to 70 ℃ then, at 75-80 ℃ of isothermal reaction 3.5 hours (temperature control is between 76-78 ℃); After isothermal reaction finishes, add three step liquid caustic soda, be warming up to 95 ℃ of timing, temperature control is in isothermal reaction between 100-105 ℃ after 1 hour, measure system viscosity once with per 15 minutes of rotational viscosimeter, reach stopped reaction between the viscosity 45-75 (centipoise/25 ℃) until system viscosity; After reaction finishes, be cooled to below 50 ℃, add silane coupling agent, stir and obtain alkalescent phenol resin after 30 minutes.
Following examples are implemented so that the application of this method to be described in conjunction with aforesaid method.
Drop into formaldehyde (37%) 812g, phenol 465g, properties-correcting agent 20g, start and stir, add step KOH (a 50%) 2g, be warming up to 60 ℃, pick up counting, and drip two step KOH (50%) 70g, dropwise in 30 minutes, be warming up to 70 ℃ then, at 75-80 ℃ of isothermal reaction 3.5 hours (temperature control is between 76-78 ℃); After isothermal reaction finishes, add three step KOH (50%) 500g, be warming up to 95 ℃ of timing, temperature control is in isothermal reaction between 100-105 ℃ after 1 hour, measure system viscosity once with per 15 minutes of rotational viscosimeter, reach stopped reaction between the viscosity 45-75 (centipoise/25 ℃) until system viscosity; After reaction finishes, be cooled to below 50 ℃, add silane coupling agent, stir and obtain alkalescent phenol resin after 30 minutes.
The synthetic alkalescent phenol resin that obtains of above-mentioned reaction is made into resin sand according to following proportioning (weight ratio), 100 parts of Da Lin standard sands (40～70 order), alkalescent phenol resin 1.8% (accounting for sand weight), glyceryl diacetate 50% (accounting for weight resin).Wherein, at first add glyceryl diacetate, mix after 1 minute, adding alkalescent phenol resin again mixed 1 minute, then this resin sand is made standard resistance to compression test block (Φ 50*50), measure 0.5 hour, 1 hour, 2 hours, 4 hours, 8 hours, 24 hours ultimate compression strength respectively, the results are shown in Table one.
Table one
Unit: MPa
Embodiment 2
| Time (h) | ??0.5h | ?1h | ?2h | ?4h | ?8h | ??24h |
| Ultimate compression strength | ??1.65 | ?2.05 | ?2.70 | ?3.32 | ?3.98 | ??4.07 |
Drop into formaldehyde (37%) 876g, phenol 495g, properties-correcting agent 20g, start and stir, add step KOH (a 50%) 2g, be warming up to 60 ℃, pick up counting, and drip two step KOH (50%) 70g, dropwise in 30 minutes, be warming up to 70 ℃ then, at 75-80 ℃ of isothermal reaction 3.5 hours (temperature control is between 76-78 ℃); After isothermal reaction finishes, add three step KOH (50%) 500g, be warming up to 95 ℃ of timing, temperature control is in isothermal reaction between 100-105 ℃ after 1 hour, measure system viscosity once with per 15 minutes of rotational viscosimeter, reach stopped reaction between the viscosity 45-75 (centipoise/25 ℃) until system viscosity; After reaction finishes, be cooled to below 50 ℃, add silane coupling agent, stir and obtain alkalescent phenol resin after 30 minutes.
The synthetic alkalescent phenol resin that obtains of above-mentioned reaction is made into resin sand according to following proportioning (weight ratio), 100 parts of Da Lin standard sands (40～70 order), alkalescent phenol resin 1.8% (accounting for sand weight), glyceryl diacetate 50% (accounting for weight resin).Wherein, at first add glyceryl diacetate, mix after 1 minute, adding alkalescent phenol resin again mixed 1 minute, then this resin sand is made standard resistance to compression test block (Φ 50*50), measure 0.5 hour, 1 hour, 2 hours, 4 hours, 8 hours, 24 hours ultimate compression strength respectively, the results are shown in Table two.
Table two
Unit: MPa
Embodiment 3
| Time (h) | ??0.5h | ?1h | ??2h | ??4h | ??8h | ?24h |
| Ultimate compression strength | ??1.78 | ?2.26 | ?2.74 | ?3.48 | ?4.01 | ?4.11 |
Drop into formaldehyde (37%) 876g, phenol 495g, properties-correcting agent 30g, start and stir, add step KOH (a 50%) 2g, be warming up to 60 ℃, pick up counting, and drip two step KOH (50%) 70g, dropwise in 30 minutes, be warming up to 70 ℃ then, at 75-80 ℃ of isothermal reaction 3.5 hours (temperature control is between 76-78 ℃); After isothermal reaction finishes, add three step KOH (50%) 500g, be warming up to 95 ℃ of timing, temperature control is in isothermal reaction between 100-105 ℃ after 1 hour, measure system viscosity once with per 15 minutes of rotational viscosimeter, reach stopped reaction between the viscosity 45-75 (centipoise/25 ℃) until system viscosity; After reaction finishes, be cooled to below 50 ℃, add silane coupling agent, stir and obtain alkalescent phenol resin after 30 minutes.
The synthetic alkalescent phenol resin that obtains of above-mentioned reaction is made into resin sand according to following proportioning (weight ratio), 100 parts of Da Lin standard sands (40～70 order), alkalescent phenol resin 1.8% (accounting for sand weight), glyceryl diacetate 50% (accounting for weight resin).Wherein, at first add glyceryl diacetate, mix after 1 minute, adding alkalescent phenol resin again mixed 1 minute, then this resin sand is made standard resistance to compression test block (Φ 50*50), measure 0.5 hour, 1 hour, 2 hours, 4 hours, 8 hours, 24 hours ultimate compression strength respectively, the results are shown in Table three.
Table three
Unit: MPa
| Time (h) | ??0.5h | ??1h | ??2h | ??4h | ??8h | ??24h |
| Ultimate compression strength | ??1.90 | ?2.45 | ?2.85 | ?3.60 | ?4.09 | ?4.26 |
Claims (9)
1. organic ester hardening alkaline phenolic resin, its composition and proportioning (weight ratio) are as follows:
Aldehydes (37.0%): 800～900 parts
Phenols (99.0%): 450～550 parts
Properties-correcting agent (98.0%): 20～40 parts
Liquid caustic soda (50%): 550～650 parts
Wherein, liquid caustic soda adds in three step modes, and the system temperature of reaction is the highest can not be above 105 ℃.
2. according to the described organic ester hardening alkaline phenolic resin of claim 1, it is characterized in that:
(a) resole is monohydric phenol and dihydric phenol and aldehyde compound and properties-correcting agent
Polycondensation obtains, and phenolic compound is that replace or non-replacement, or their mixture.
(b) alkaline compound solution comprises sodium hydroxide, the basic cpd that potassium hydroxide and Al family metallic element form.
(C) mixture of silane coupling agent and above-mentioned resole, ratio are 0.01%～2%.
(d) weight-average molecular weight of the resin that obtains of above-mentioned phenols and aldehyde compound copolycondensation is 400 to 4000.
3. according to the described organic ester hardening alkaline phenolic resin of claim 1, wherein aldehyde compound is an alkanoic.
4. according to the described organic ester hardening alkaline phenolic resin of claim 1, wherein phenolic compound is to select in phenol, cresols, nonyl phenol, a first diphenol or mixture cresol.
5. according to the described organic ester hardening alkaline phenolic resin of claim 1, wherein properties-correcting agent is ketone compound.
6. according to the described organic ester hardening alkaline phenolic resin of claim 1, wherein silane coupling agent is selected in γ-An Bingjisanjiayangjiguiwan, γ-(2-amino) aminopropyl methyl-monosilane, γ-An Bingjisanyiyangjiguiwan, alpha-oxidation glycidyl propyl trimethoxy silicane.
7. described according to claim 3, wherein aldehyde compound is to select in formaldehyde, Paraformaldehyde 96, acetaldehyde or oxalic dialdehyde.
8. according to the described organic ester hardening alkaline phenolic resin of claim 1, resin weight-average molecular weight wherein is 500 to 4000.
9. the manufacture method of organic ester hardening alkaline phenolic resin is characterized in that:
(1) phenol is dissolved with after aldehyde, properties-correcting agent mix, add a step alkali;
(2) be warming up to 60 ℃, drip two step alkali;
(3) be warming up to 70 ℃, isothermal reaction;
(4) add three step liquid caustic soda, isothermal reaction between 100-105 ℃;
(5) be cooled to below 50 ℃ termination reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01127451 CN1410466A (en) | 2001-09-29 | 2001-09-29 | Organic ester hardening alkaline phenolic resin and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01127451 CN1410466A (en) | 2001-09-29 | 2001-09-29 | Organic ester hardening alkaline phenolic resin and its preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1410466A true CN1410466A (en) | 2003-04-16 |
Family
ID=4667406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01127451 Pending CN1410466A (en) | 2001-09-29 | 2001-09-29 | Organic ester hardening alkaline phenolic resin and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1410466A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101208368B (en) * | 2005-07-13 | 2011-02-09 | 宇部兴产株式会社 | Biphenylene-bridged phenol novolak resins and use thereof |
| CN103059505A (en) * | 2012-11-23 | 2013-04-24 | 沈阳铸造研究所 | CO2 cured alkaline phenolic resin and preparation method thereof |
| RU2480308C1 (en) * | 2010-02-11 | 2013-04-27 | Цзинань Шэнцюань Груп Шеа-Холдинг Ко., Лтд. | Phenol resin-based adhesive composition |
| CN108947546A (en) * | 2018-07-20 | 2018-12-07 | 绍兴上虞自强高分子化工材料有限公司 | A kind of fire bond and its preparation method and application |
| CN114669718A (en) * | 2020-12-24 | 2022-06-28 | 金隆化学工业股份有限公司 | Method for manufacturing adhesive material lamination |
-
2001
- 2001-09-29 CN CN 01127451 patent/CN1410466A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101208368B (en) * | 2005-07-13 | 2011-02-09 | 宇部兴产株式会社 | Biphenylene-bridged phenol novolak resins and use thereof |
| RU2480308C1 (en) * | 2010-02-11 | 2013-04-27 | Цзинань Шэнцюань Груп Шеа-Холдинг Ко., Лтд. | Phenol resin-based adhesive composition |
| CN103059505A (en) * | 2012-11-23 | 2013-04-24 | 沈阳铸造研究所 | CO2 cured alkaline phenolic resin and preparation method thereof |
| CN103059505B (en) * | 2012-11-23 | 2015-06-10 | 沈阳铸造研究所 | CO2 cured alkaline phenolic resin and preparation method thereof |
| CN108947546A (en) * | 2018-07-20 | 2018-12-07 | 绍兴上虞自强高分子化工材料有限公司 | A kind of fire bond and its preparation method and application |
| CN108947546B (en) * | 2018-07-20 | 2021-09-07 | 浙江自立高分子化工材料有限公司 | Refractory material binder and preparation method and application thereof |
| CN114669718A (en) * | 2020-12-24 | 2022-06-28 | 金隆化学工业股份有限公司 | Method for manufacturing adhesive material lamination |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1219985A (en) | Foundry moulds and cores | |
| US9993863B2 (en) | Low-emission cold-setting binder for the foundry industry | |
| EP2418030B1 (en) | Curing agent composition | |
| US5032642A (en) | Phenolic resin compositions | |
| CA1123529A (en) | Acid-curable fluoride-containing resin molding composition | |
| JP2011520615A (en) | Methanesulfonic acid-containing catalyst in acid curing process | |
| JP2006518667A (en) | Method for producing cores, molds and feeders for use in molded objects, in particular in casting technology | |
| JP2012533433A (en) | Casting binder containing one or more cycloalkanes as solvent | |
| CN1410466A (en) | Organic ester hardening alkaline phenolic resin and its preparation method | |
| CN101348549A (en) | Hydroxyl-terminated alkaline phenolic resin and preparation thereof | |
| CN103059505A (en) | CO2 cured alkaline phenolic resin and preparation method thereof | |
| US3755229A (en) | Foundry core compositions | |
| JP2003525748A (en) | Binder for furan-no-bake casting and its use | |
| JP6216637B2 (en) | Self-hardening mold manufacturing method, mold binder kit, and mold composition | |
| JPS62282743A (en) | Phenol formaldehyde resin binder | |
| CN113891771B (en) | Adhesive composition for casting mold | |
| CN1017316B (en) | Resin sand for foundry | |
| JP4398299B2 (en) | Organic binder for mold, foundry sand composition obtained using the same, and mold | |
| JP3249010B2 (en) | Manufacturing method of casting mold | |
| WO2023054430A1 (en) | Mold composition | |
| JP3165262B2 (en) | Binder composition for casting, composition for casting, and method for producing casting mold | |
| JP3131038B2 (en) | Binder composition for casting, composition for casting, and method for producing casting mold or core | |
| JP2542144B2 (en) | Binder composition for organic ester-curable foundry sand and method for producing mold using the same | |
| WO1997049513A1 (en) | Caking additive composition for forming self-hardening mold | |
| JP2006289467A (en) | Composition of binding agent for making casting mold, composition for making casting mold, and method for manufacturing casting mold |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C57 | Notification of unclear or unknown address | ||
| DD01 | Delivery of document by public notice |
Addressee: Liu Yanping Document name: Notice of first review |
|
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |